Removal of Cobalt (II) from Aqueous Solutions by Adsorption on Low cost activated carbon

Removal of Cobalt (II) from Aqueous Solutions by Adsorption on Low cost activated carbon R.PRABAKARAN #$ S.ARIVOLI * $ Department of chemistry, Centre for Research and Development, PRIST University, Vallam, Thanjore (District), Tamilnadu, India. # Mount Zion College of Engineering and Technology, Pudukkottai, * Department of chemistry, Thiru.Vi.Ka. Ka Government Arts College, Thiruvarur, India Abstract In this research work, activated carbon prepared locally from Thespesia Populnea bark(tpc) was examined for the removal of cobalt (II) from aqueous solution. The main parameters, like effect of adsorbent dosage, Co (II) concentrations, effect of contact time and effect of ph was studied in batch experiments. The experimental results were analyzed by using Langmuir, Freundlich, adsorption isotherm models. The kinetic data well described by the pseudo-first-order kinetic model. The various thermodynamic parameters such as, and were also determined. The activated carbon produced from TPC was successfully employed for removal of cobalt (II) ion from aqueous solution and the technique appears industrially applicable and feasible. Keywords: cobalt (II) ions, adsorption, kinetic, isotherm Notations C i initial concentration of adsorbate (mol/l) R Gas constant (8.1314) T Temperature in Kelvin Enthalpy Entropy Free energy Abbreviation TPC -Thespesia Populnea Bark Carbon Introduction The safety our environment has been continuously rapid increase in urbanization, industrialization and human activities [1] Heavy metals are toxic pollutants released into the surface and ground water as a result of various activities such as industries, mining and agriculture [2]. The rapid pace of industrialization has led to severe problem of water pollution. Heavy metals can easily enter the food chain because of 271

their high solubility in water. These heavy metals may include copper, iron, zinc, cadmium, lead, cobalt etc. Thus taking into account the harmful effect of these heavy metals, that causes a number of health problems, diseases and disorders [3] Cobalt (II) compounds are essential in many industries. Their applications in nuclear power plants, metallurgy, mining, pigments, paints and electronic are only few examples where the presence of cobalt in attractive force between the molecules. In this study, the batch experiments were conducted in order to investigate the removal of cobalt (II) ions from aqueous solutions using locally prepared activated carbon from Thespesia Populnea bark (TPC). Material and methods Adsorbent preparation Adsorbent (Activated Carbon Fig 1) has been produced by using air-dried Thespesia waste waters represents a major Populnea bark with con.sulphuric acid in a environmental problem [4, 5]. The treatment technologies more frequently cited for removal of heavy metals are carbon weight ratio of 1:1. Then the product was heated in a furnace at 500 C for 12 hours and followed by washing with water until adsorption, wet oxidation, solvent free from excess acid and dried at 150 ± extraction, precipitation, ultra filtration, reverse osmosis, ion-exchange, etc[6]. 5 C. The dried material was ground well to fine powder and sieved. Among these options, adsorption is most preferred method and activated carbon is most effective adsorbent widely employed to treat wastewater containing different classes of metal ions/dyes, recognizing the economical drawback of commercial activated carbon. Activated carbon has been quite successful for removal of impurities from exhaust gas and waste water streams. The highly porous nature of the carbon Fig (1) Activated Carbon Batch equilibrium method: The adsorption of cobalt (II) ion on TPC was studied by batch technique. The provides a large surface area for experiments were done at various contaminants to get deposited. The temparature such as 30, 40, 50 and 60ºC in adsorption takes place because of the batch process. 272

The experiments were carried out in Table 1-Characteristics of the Adsorbent different 100 ml iodine flasks. Prior to each experiment, a predetermined amount of Sl. No Properties TPC absorbent was added to each flask. The 1 Particle size(mm) 0.041 stirring was kept constant at 120 rpm. Each 2 Density (g/cc) 0.3243 flask was filled with a known amount of 3 Moisture content (%) 0.3255 sample before commencing stirring such as 4 Loss in ignition (%) 0.273 metal solutions with an initial concentration of 5 mg/l to 25 mg/l. The flask containing 5 ph of aqueous solution 6.5 the sample was withdrawn from the shaker Effect of contact time and initial Cobalt at the predetermined time interval, filtered (II) ion concentration and the residual of the metal ion concentration has been measured. Results and discussion The effect of contact time on Cobalt (II) adsorption on TPC was investigated to study about the rate of removal of cobalt ion. Fig. Characteristics of the adsorbent The physico chemical properties of the adsorbent are listed in Table1. 2 shows that the percentage removal of Cobalt (II) for various values of initial Co ion concentration ranging from 5 to 25mg/L. From Fig. 2, indicated that, the percentage of Cobalt (II) ions removed at 5, 10, 15, 20 and 25 mg/l levels from 25 to 61 respectively. As the concentration of metal ion increases, more and more surface sites are covered and hence at higher concentrations of metal ions the capacity of the adsorbent get exhausted due to nonavailability of the surface sites [7].It is therefore evident that at low concentration ranges the percentage of adsorption is high because of the availability of more active sites on the surface of the adsorbent. 273

Fig. 2- Effect of Contact time on the Fig. 3- Effect of Adsorbent dose on the adsorption of Cobalt (II) ion onto TPC adsorption of Cobalt ion onto TPC [Cobalt] = 50 mg/l: Adsorbent dose = 25mg/ 50ml: ph=6.5 Effect of adsorbent dose The results for adsorptive removal of cobalt ions with respect to adsorbent dose are shown in Fig. 3. The adsorption of Cobalt ion on adsorbent was studied by varying the carbon concentration from 5 to 25 mg/50 ml while keeping the cobalt ion concentration as 50mg /L. From Fig. shows that the increase in adsorbent dosage from 5 to 25 mg/50 ml resulted in an increase from 73 to 86% in adsorption of cobalt ion. It is due to the availability of high binding sites for complexation of cobalt ions [8]. The equilibrium values were showed in Table.2. [Cobalt] = 50mg/L: contact time = 60min: ph=6.5 Adsorption isotherms Adsorption isotherm study was done by four different temperatures which were are 30, 40, 50 and.two most common isotherm models were used for describing the adsorption data, which were Langmuir and Freundlich isotherm. The Langmuir equation can be represented in the form of following equations. C eq /Q eq = 1/Q m b + Ceq/Q m (1) Where C eq is the equilibrium concentration of cobalt ion in solution (mg/l), Q eq is the amount of cobalt ion adsorbed; Q m and b is Langmuir constants related to adsorption efficiency and energy of adsorption, respectively. 274

Table 2 Equilibrium parameters for the adsorption of Co (II) ions onto activated carbon Cobalt ion ( mg/l) Temperature C C e (mg/l) Q e (mg/g) Removal of Cobalt ion (%) 30 40 50 60 30 40 50 60 30 40 50 60 5 0.272 0.223 0.181 0.155 9.457 9.554 9.638 9.689 94.57 95.54 96.38 96.89 10 1.459 1.253 0.975 0.776 17.08 17.49 18.05 18.45 85.41 87.47 90.25 92.24 15 3.285 2.825 2.384 1.994 23.43 24.35 25.23 26.01 78.10 81.16 84.11 86.70 20 8.755 8.172 7.559 6.953 22.49 23.66 24.88 26.09 56.23 59.14 62.20 65.24 25 14.19 13.46 12.72 12.04 21.61 23.08 24.57 25.91 43.22 46.17 49.14 51.83 Table.3 Langmuir Isotherm, Freundlich Isotherm results and Dimensionless Separation factor for adsorption of Co(II) ion onto TPC Cobalt ion, (mg/l) Temp ºC Langmuir Isotherm Freundlich Isotherm Dimensionless Separation Factor(R L ) Statistical parameters Statistical parameters [ Cobalt ion] ( mg/l) r 2 Q m b r 2 K f n 5 10 15 20 25 30 0.9911 22.271 5.045 0.9231 3.181 4.618 0.038 0.019 0.013 0.008 0.006 40 0.9912 23.752 4.480 0.9272 3.266 4.528 0.036 0.021 0.014 0.011 0.007 50 0.9931 25.188 4.616 0.9331 3.368 4.512 0.041 0.021 0.014 0.010 0.007 60 0.9913 26.525 4.773 0.9342 3.459 4.466 0.040 0.020 0.013 0.010 0.006 275

The linear plots of Ceq/ Q eq vs. C eq suggest the applicability of the Langmuir isotherms Fig. 4. The values of Q m and b were calculated from slope and intercepts of the plots are given in Table 3. From the results, it is indicates that the value of adsorption efficiency Q m and adsorption energy b of the (mg/l), and K f and n are constant integrates, the factors affecting the adsorption capacity and intensity of adsorption, respectively. Linear plots of log Q e versus log C e shows that the adsorption of cobalt ion obeys the Freundlich adsorption isotherm. In Fig.5, the Freundlich adsorption isotherm obtained by carbon increases on increasing the plotting C e / q e versus C e for the adsorption temperature. The values can conclude that of cobalt (II) on TPC at the different the maximum adsorption corresponds to a temperatures investigated, respectively. saturated monolayer of adsorbate molecules on adsorbent surface with constant energy and no diffusion of adsorbate in plane of the The K f and n values are given in Table 3, which indicate that the increase of negative charges on the adsorbent surface makes adsorbent surface. To confirm the electrostatic force like Vander Waal s favourability of the adsorption process, the between the carbon surface and cobalt ion. separation factor (R L ) was determined and The values clearly indicate the dominance in listed in Table 3. The values were adsorption capacity. The intensity of established to be between 0 and 1 and adsorption is an indication of the bond confirm that the ongoing adsorption process energies between metal ion and adsorbent, is favorable[9].the Freundlich isotherm is and the possibility of slight chemisorptions generally represented by the following rather than physisorption [10, 11]. However, equation. the multilayer adsorption of cobalt ion log Q e = log K f +1/n log C e (2) through the percolation process may be possible. The values of n are less than one, Where Q e is the amount of cobalt ion adsorbed (mg/g), C e is the equilibrium indicating the physisorption is much more possible [12]. concentration of cobalt ion in solution 276

Table 4 Equilibrium parameters for the adsorption of Cobalt ions onto TPC Cobalt ion (mg/l) 5 Temperature C C e (mg/l) Q e (mg/g) Removal of Cobalt ion (%) 30 40 50 60 30 40 50 60 30 40 50 60 0.272 0.223 0.181 0.155 9.457 9.554 9.638 9.689 94.57 95.54 96.38 96.89 10 1.459 1.253 0.975 0.776 17.08 17.49 18.05 18.45 85.41 87.47 90.25 92.24 15 3.285 2.825 2.384 1.994 23.43 24.35 25.23 26.01 78.10 81.16 84.11 86.70 20 8.755 8.172 7.559 6.953 22.49 23.66 24.88 26.09 56.23 59.14 62.20 65.24 25 14.19 13.46 12.72 12.04 21.61 23.08 24.57 25.91 43.22 46.17 49.14 51.83 Fig. 4- Langmuir Isotherm for the adsorption of cobalt ion onto TPC Fig 5- Freundlich Isotherm for the adsorption of cobalt ion onto TPC 277

Thermodynamic studies The experiments were done at different temperatures of 30, 40, 50 and 60. Variable thermodynamic parameters such as change in free energy ( G ) (kj/mol), enthalpy ( H ) (kj/mol) and entropy ( S ) (J/K mol) were determined by the following equations.. K 0 = C solid / Cliquid G = -RT lnk O logk 0 = S / (2.303R) - H /(2.303RT) Where K o is the equilibrium constant, C solid is the solid phase concentration at equilibrium (mg/l), C liquid is the liquid phase concentration at equilibrium (mg/l), T is the temperature in Kelvin, and R is the gas constant. The H and S values obtained from the slope and intercept of Van t Hoff plots are given in Table 4.The values of H is in the range of 1 to 93 kj/mol indicates the favorability of physisorption. It is very clear that from the results that physisorption is much more possible for the adsorption for cobalt ion. The positive values of H indicate the endothermic nature of adsorption and it governs the possibility of physical adsorption[12,13]. The negative values of G are given in Table 4 indicate that the adsorption is greatly favorable for cobalt ion. The positive values of S in Table 4 shows the increased disorder and randomness at the solid solution interface of cobalt ion with TPC adsorbent. The results indicate that more efficient physisorption[11, 14 and 15]. Table 5 Equilibrium constant and thermodynamic parameters for the adsorption of Cobalt ion onto TPC Cobalt ion (mg/l) H S Temperature ( C) K 0 G 30 40 50 60 30 40 50 60 5 16.474 78.149 17.41 21.44 26.59 31.17-7198.2-7976.9-8810.0-9522.8 10 20.147 80.919 5.855 6.984 9.259 11.89-4452.2-5057.9-5976.8-6854.9 15 16.890 66.219 3.566 4.309 5.291 6.521-3203.2-3801.2-4474.3-5191.2 20 10.620 37.015 1.284 1.447 1.645 1.876-630.74-962.16-1337.5-1742.6 25 9.7019 29.741 0.761 0.858 0.966 1.076-687.22-399.33-92.817-202.31 278

Adsorption kinetics The kinetics of removal of Co (II) using TPC as an adsorbent, pseudo first order, has been tested with the experimental data. The sorption of cobalt ions on TPC may involve chemical sorption which can control the chemical reaction rate. The removal of cobalt ion from an aqueous solution obeys the reversible first order kinetics, when a single species considered on a heterogeneous surface. At equilibrium, the rate is the ratio of the concentration of adsorbate in adsorbent and concentration of adsorbate in aqueous solution given by K 0. The results indicate that K 0 values decreases with increase in the concentration of the cobalt ion and increases with increase in temperature. The calculated values are listed given in the Table 4. The heterogeneous equilibrium between the cobalt ion solution and the activated carbon are represented as A k 1 k2 Where k 1 is the forward rate constant and k 2 is the backward rate constant. A indicate the cobalt ion remaining in the aqueous solution and B indicate that cobalt ion adsorbed on the surface of activated carbon. The rate constants calculated as earlier [10, 11 and 16]. The data are specified in Table 5, shows that the forward rate constant is much higher than the backward rate constant suggesting that the rate of adsorption is clearly dominant. B Table 6- Rate constants for the adsorption of metal ion (10 3 k ad, min -1 ) and the constants for forward (10 3 k 1, min 1) and reverse (10 3 k 2, min -1 ) process. Temperature ( C) Cobalt ion mg/l k ad k 1 k 2 k 1 k 2 k 1 k 2 k 1 k 2 30 40 50 60 30 40 50 60 5 0.057 0.061 0.065 0.070 0.054 0.003 0.058 0.002 0.063 0.002 0.068 0.002 10 0.032 0.035 0.040 0.046 0.027 0.004 0.030 0.004 0.036 0.003 0.042 0.003 15 0.025 0.027 0.030 0.033 0.019 0.005 0.021 0.005 0.025 0.004 0.028 0.004 20 0.019 0.020 0.022 0.023 0.010 0.008 0.011 0.008 0.013 0.008 0.015 0.008 25 0.016 0.017 0.019 0.020 0.007 0.009 0.008 0.009 0.009 0.009 0.010 0.009 279

A clear examination of the effect of cobalt speciation and solubility of metal ions[18]. ion concentrations on the rate constant K ad The effect of ph on the removal of cobalt (Table 5), the values help to describe the ion using TPC as an adsorbent was studied mechanism of metal ion adsorption taking with initial ph range from 3-11. The relation place.in cases of strict surface adsorption a between the initial ph of the solution and variation of rate should be proportional to percentage removal of cobalt ion is depicted the first power of concentration. However, in Fig. 6. As can be seen from Figure when pore diffusion limits the adsorption observed that the percentage adsorption process, the relationship between initial Cobalt ions increased appreciably (1-2 cobalt ion concentration and rate of reaction times) with increase of ph from 3 to 6.5 and will not be linear. It shows that pore consistent with results obtained by others. diffusion limits the overall rate of cobalt ion Effect of the other ion adsorption[12, 17]. The effect of other ion like Cl - on the adsorption Effect of ph process was studied at various concentrations. The solution of ph is an important The effect of sodium chloride on the adsorption parameter in the adsorption process of metal of cobalt ion on TPC is shown in Fig. 7. The low ions from aqueous solutions, which affect concentrate NaCl solutions have slight influence both the dissociation degree of functional on the adsorption capacity. groups from adsorbent surface and the Fig. 6- Effect of ph on the adsorption of cobalt ion onto TPC [Co]= 20mg/L: adsorbent dose = 25 mg / 50ml: contact time = 60min Fig. 7- Effect of other ions on the removal of Cobalt ion onto TPC [Co] = 20mg/L: adsorbent dose = 25 mg / 50ml: contact time = 60ml 280

When the concentration of NaCl increases, in agreement with the ph dependent results the ionic strength is increased. At higher obtained. Desorption of metal ion by ionic strength, the adsorption of cobalt ion mineral acids and alkaline medium indicates will be high due to the partial neutralization that the metal ion was adsorbed onto the of the positive charge on the carbon surface activated carbon through by physisorption and a consequent compression of the mechanism[20]. electrical double layer by the Cl - anion. The Conclusions chloride ion also enhances adsorption of cobalt ion by pairing their charges, and hence reducing the repulsion between the removal of cobalt ions on the surface. This initiates carbon to adsorb more positive cobalt ions [19, 20]. Desorption studies Disposal of the exhausted adsorbent loaded with metal ions produce another environmental problem, as it is toxic material, which pollutes the environment. Therefore regeneration of the adsorbent material is of crucial importance in economic development. Desorption studies helps to illuminate the nature of the adsorption process and the recovery of metal ion from TPC. The reuse of regenerated activated carbon was found to be efficient. The effect of various reagents used for desorption studies indicate that hydrochloric acid is a better reagent for desorption, because more than 90% removal of adsorbed metal ion takes place. The reversibility of adsorbed metal ion in mineral acid or base is This research work proved that applicability of Thespesia Populnea bark were excellent low cost biosorbent for the removal of cobalt ions. The adsorption process was greatly based on solution of ph and effect of temperature. The kinetic study of Co (II) ion sorption on TPC was followed Pseudo- first order kinetic model. The process of adsorption was tested by the Lanqmuir than Freundlich model. The thermodynamic parameters such as, and clearly indicates the spontaneous and endothermic nature of the adsorption process. Reference [1] J.Rivera Utrilla, M.A. Ferro- Garcia, M.D. Mingorance and I.Bautista-Toledo, Adsorption of lead on activated carbons from olive stones. J. Chem. Technol. Biotechnol., 1988. 36: 47-52. [2]. S. Bounheng,; N.; Kazunori, N. Munehiro, C. Nobou, N. Osamu, Water Res. 2006, 40, 2295. 281

[3]. WHO, Guidelines for Drinking Water [10]. S. Arivoli, M. Viji Jam, and T. Quality, World Health Organization, Rajachandrasekar, Cobalt Adsorption on a Geneva, 2006. [4]. D.L. Baun and T.H.Christensen. Speciation of heavy metals in landfill Low Cost Carbon-Kinetic, Equilibrium and Mechanistic Studies, Mat Sci Res India,3, 2006, pp. 241-250. leachate: a review. Waste Manage. Res. Vol. 22, 2004, pp. 3 23. [5]. S. Babel and T.A.Krniavan. Low cost adsorbants for the heavy metals uptake from contaminated water: a review. J. Hazard. Mater. Vol. B 97, 2003, pp. 219 243. [6]. T.A. Kurniawan Chan, G.Y.S., Lo, [11]. C. Namasivayam R. Jeyakumar, R.T.Yamuna, J. Jayanthi, dye removal from waste water by adsorption on waste Fe (III), Cr (III) hydroxide, Waste Manage. 14, 1994 643 648. [12]. S. Arivoli, B. R. Venkatraman, T. Rajachandrasekar, and M. Hema, W.H., Babel, S. Physico-chemical Adsorption of Ferrous Ion from Aqueous treatment techniques for wastewater Solution by Low Cost Activated Carbon laden with heavy metals, Chemical Obtained from Natural Plant Material, Res Engineering Journal, 2006, 118, pp 83-98. [7]. C. Namasivayam, N. Muniasamy, M. J Chem Environ.17, 2007, pp. 70 78 [13]. D. G. Krishna and G. Bhattacharyya, Gayathri, M. Rani K.Renganathan Adsorption of Methylene Blue on Removal of Dyes from Aqueous solution by Kaolinite, Appl Clay Sd, 20, 2002, p. 295. cellulosic waste orange peel, Biores. [14]. K.A. Krishnan, T.S. Anirudhan. Technol., 1996, 57, p.37. Removal of Cadmium (II) from aqueous solutions by team- activated sulphurised [8]. M. Mohapatra, T. Padhi, T. Dash, P Carbon Prepared from sugar Cane bagasse Sing, S. Anand, and B.K.Mishra,. Cation pith: Kinetics and equilibrium studies. Water sorption on nano structured high surface SA 29(2), 147, 2003. area 6 line ferrihydrite, J. Hazard.Mater. 2009, 148 (3)553-559. [15] S. Arivoli, K. Kalpana, R. Sudha, and T. Rajachandrasekar, Comparative Study [9]. C.Namasivayam R.T Yamuna. on the Adsorption Kinetics and adsorption of direct dye red dye biogas Thermodynamics of Metal Ions onto Acid residual slurry, environ. Pollut. 1995, 89p.1 282

Activated Low Cost Carbon, E J Chem, 4, 2007, pp. 238 254. [16] W.J. Weber, Principle and Application of Water Chemistry, ed. S.D. Faust and J.V. Hunter. New York: Wiley, 1967. [17] Renmin Gong, Yingzhi Sun, Jian Chen, Huijun Liu, and Chao Yang, Effect of Chemical Modification on Dye Adsorption Capacity of Peanut Hull, Dyes and Pigments, 67, 2005, p. 179. [18]. Ma W. and Tobin J.M., Determination and modelling of effects of ph on peat biosorption of chromium, copper and cadmium. Biochem. Eng. J. Vol. 18, 2004, pp. 33 40. [19] B. Zhu, T. Fan, D. Zhang, Adsorption of copper ion from aqueous solutions by citric acid modified soybean straw. Journal of hazardous materials 153, 2008, 300-308. [20] M K. Sreedhar and T S.Anirudhan, Indian J environ protect, 1999, 19, 8. 283